Polyols for urethane-modified isocyanurate foams

ABSTRACT

A method for the manufacture of urethane-modified polyisocyanurate foams in which an isocyanate is blended with a &#34;B&#34; side comprising a polyol blend, a surfactant, a blowing agent, and a catalyst. The polyol blend comprises at least 5% (wt.) of a mixture of a polyalkoxylated amine and a polyalkoxylated quaternary ammonium borate ester, at least 40% (wt.) of a resin polyol, with any remainder being a polyether or polyester polyol. All components of the &#34;B&#34; side will remain a homogeneous liquid without phase separation and without the need for agitation for at least 3 days after blending. The resin polyols are preferably moderate viscosity, aromatic polyester polyols derived from polycarbomethoxyl-substituted diphenyls, polyphenyls, and benzyl esters of the toluate family.

BACKGROUND OF THE INVENTION

This invention pertains to the formation of urethane-modifiedisocyanurate foams using mixtures of polyalkoxylated amines andpolyalkoxylated quaternary ammonium borate esters as copolyols. Moreparticularly this invention relates to the use of such copolyols to formfoams having NCO/OH ratios of 1.5 to 3.5, using very inexpensive,commercially available resin polyols. A blend of these polyalkoxylatedamines and polyalkoxylated quaternary ammonium borate esters with theaforesaid resin polyol and, optionally, a polyether or polyester polyolis very stable and will remain a homogeneous liquid without phaseseparation and without the need for agitation for at least 3 days afterblending and usually, for at least 7 days.

Urethane and polyisocyanurate foams are manufactured using a blend of anisocyanate and a polyol. The molar ratio of isocyanate to polyol, thatis, the ratio of NCO functional groups to OH functional groups, is knownas the "index" or "NCO/OH ratio". Foams are manufactured with bothisocyanates and polyols and when the molar ratio of isocyanate to polyolis between 1.05 to 1.15, a urethane foam is formed according to thereaction: ##STR1##

The urethane product shown above is the monomeric structural unit thatcombines to form the polyurethane foam. At an index between 1.5 and 3.5,a urethane-modified isocyanurate foam is formed. At indices above 4.0,an isocyanurate foam is formed having the monomeric unit: ##STR2## whichmay have a minority of urethane linkages. Herein, the terms isocyanurateand polyisocynurate and the terms urethane and polyurethane in referenceto foams will be used inter-changeably.

Currently, urethane-modified polyisocyanurate foams are manufacturedusing polyether or polyester polyols, as for example the Voranol® groupof polyols available from Dow Chemical Company, Midland, Mich. Whencombined with a catalyst, a surfactant, and a blowing agent, and thenwith an isocyanate in the known manner, these polyether or polyesterpolyols form a foam having good qualities. Certain resin polyols, suchas the Terate® resin polyol available from Hercules, Incorporated,Wilmington, Del. are of a hydroxyl number sufficient so as totheoretically permit their use in foam manufacture. In practice,however, these polyols have proved to be unacceptable at concentrationsin excess of 40% (wt.) of the total polyol blend for use inmanufacturing high quality urethane-modified polyisocyanurate foams.Because the resin polyols are about one-third less costly than thecurrently used conventional polyether or polyester polyols, it isdesirable that a polyol blend be found that may be used with largerquantities of such resin polyols to result in a polyisocyanurate foamhaving acceptable properties and at a lower cost.

SUMMARY OF THE INVENTION

The present invention is a method for the manufacture ofurethane-modified polyisocyanurate foams, comprising blending anisocyanurate with a "B" side, the "B" side comprising a polyol blend, asurfactant, a blowing agent, and a catalyst if one is used. The polyolblend comprises: at least 5% (wt.) of a mixture of a polyalkoxylatedamine and a polyalkoxylated quaternary ammonium borate ester, the weightratio of the polyalkoxylated amine to the polyalkoxylated quaternaryammonium borate ester being between 1:0.005 and 1:12; at least 40% (wt.)of a resin polyol, the resin polyol comprising at least 70% (wt.) of acombination of polymers and monomers having the general formula:##STR3## wherein n is between 0 and 50, R₁₁ is H-- or CH₃ --, and p andq are integers each having a value of between 1 and 10; and theremainder of the polyol blend being a polyether or polyester polyol. Apreferred ratio of amine to quaternary borate ester is the range from1:0.1 to 1:4. All of the components of the "B" side may be blended andwill thereafter remain a homogeneous liquid without phase separation andwithout the need for agitation for at least three days.

In another embodiment of the invention, the polyalkoxylated amine isselected from the group consisting of: ##STR4## wherein R is selectedfrom the group of alkyl radicals having between 1 and 18 carbon atoms, xand y are integers each having a value of at least one and wherein hesum of x and y does not exceed 50 and wherein R₁ and R₂ may be the sameor different and may be selected from the groups consisting of H--, CH₃--, C₁ -C₁₀ straight- or branched-chain alkyl or alkenyl radicals, aphenyl group, a benzyl group or halogenated alkyl group. In a mostpreferred polyalkoxylated amine, R corresponds to the tallow alkylgroup, R₁ and R₂ are each H--, and x plus y equal 5. Hence, thepreferred polyalkoxylated amine is a tallow penta-ethoxylated amine.

In a still further embodiment of the invention, the polyalkoxylatedquaternary ammonium borate esters are of the general formula: ##STR5##wherein R₃ is a straight- or branched-chain alkyl or alkenyl radicalhaving from 1 to 30 carbon atoms, inclusive, or a phenyl or benzylradical; R₄ is H--, a C₁ to C₁₀ straight- or branched-chain alkyl oralkenyl radical, a phenyl group, a benzyl group, or a halogenated alkylgroup; R₅ and R₆ are different or the same and are selected from thegroup including H--, or a C₁ to C₁₀ straight- or branched-chain alkyl oralkenyl radical, a phenyl group, or a benzyl group; and wherein m is aninteger between 0 to 30, inclusive. Preferably, the polyalkoxylatedquaternay ammonium borate ester will include an R₃ that is a straight-or branched-chain alkyl or alkenyl radical having from 8 to 18 carbonatoms, and R₄, R₅, R₆ will be H--. The borate ester anion mayalternatively include a CH₃ -- at the R₆ position. A most preferredquaternary ammonium borate ester has an m equal to 0 and an R₃corresponding to the tallowalkyl (C₁₈ H₃₇) radical.

In yet another embodiment of the present invention, the polyalkoxylatedamine is selected from the group consisting of: ##STR6## wherein R₇ isselected from the group of C₁ -C₂₀ alkyl groups and R₈ is a C₂ to C₅alkyl group; R₁ and R₂ are the same or different and may be selectedfrom the groups consisting of H--, CH₃ --, C₁ to C₁₀ straight- orbranched-chain alkyl or alkenyl radicals, a phenyl group, a benzylgroup, or a halogenated alkyl group, and x and y are integers eachhaving a value of at least 1 and having a sum not exceeding 50.

An object of the present invention is a method for the manufacture ofurethane-modified polyisocyanurate foams in which the polyol blend,surfactant, blowing agent, and catalyst remain a homogeneous liquidwithout phase separation and without the need for agitation for at leastthree days. A further object of the invention is a method for themanufacture of urethane-modified polyisocyanurate foams in which atleast 40% and preferably in excess of 65% by weight of the polyol blendcomprises a resin polyol so as to reduce the cost of manufacturing thosefoams by decreasing the amount of relatively expensive conventionalpolyether or polyester polyol used in the polyol blend.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The isocyanates may be selected from the groups including the organicpolyisocyanates which are disclosed herein as useful in the productionof conventionally manufactured polyisocyanurate foams. A preferredpolyisocyanate is Mondur® MR, a polycyclic aromatic polyisocyanateavailable from the Mobay Chemical Corporation, Pittsburgh, Pa.

Present polyisocyanurate foams may be manufactured according to methodsknown in the art. These methods comprise blending two components,stirring, and allowing the blend to rise in an open container so as toform the desired foam. The two components are known as the "A" and "B"components, or "sides", with the "A" component comprising the isocyanateand the "B" component comprising a blend of polyol, catalyst, surfactantand blowing agent. A catalyst may be used, but is not essential.

Catalysts, if used, may be selected from those conventionally used inthe art, including metal salts, alkali metal salts, and tertiary aminetrimerization catalysts. A preferred catalyst is potassium octanoate orpotassium 2-ethylhexanoate. The present preferred catalyst is M & T-T-45catalyst, which is 45% active potassium 2-ethylhexanoate and 55%polyethylene glycol having a molecular weight of 200, and which isavailable from M & T Chemicals Inc., Rahway, N.J., 07065. The amount ofcatalyst to be used may be up to 20% of the total polyol blend weight,but much less may be used and is desirable from an economic standpointto use lower amounts, preferably less than 2.0% and more preferably lessthan 1.5%. The blowing agent may be selected from the group includingwater, methylene chloride, or any of the fluorocarbons known to thoseskilled in the art which can be used for blowing polymer mixtures intocellular polymers. Generally speaking, such fluorocarbon blowing agentsare fluorinated aliphatic hydrocarbons which may also be substituted bychlorine and/or bromine. A most preferred blowing agent is Freon® 11A, atrifluorochloromethane produced by E. I. DuPont de Nemours & Company,Wilmington, Del. Surfactants may likewise be chosen from among thoseknown to the skilled in the art; a preferred surfactant is DC-193, asurfactant having silicon glycol copolymers with direct silicon-carbonbonds, and sold by the Dow Corning Corporation, Midland, Mich.

The present polyol blends may be obtained by mixing in a container thepolyalkoxylated amine, polyalkoxylated quaternary ammonium borate ester,resin polyol, and optionally, the polyether or polyester polyol. Thepolyalkoxylated amines may include polyethoxylated or polypropoxylatedamines, wherein the amines are tertiary amines having one fatty alkylgroup derived from various fatty sources and two or more polyoxyethyleneor polyoxypropylene groups attached to the nitrogen. Typical of thesepolyethoxylated or polypropoxylated amines are the Ethomeen®polyethoxylated amines available from the Akzo Chemie America, 300 SouthWacker Drive, Chicago, Ill. 60606, preferably being of the generalformula: ##STR7## wherein R is selected from the group of alkyl radicalshaving between 1 and 18 carbon atoms, x and y are integers each having avalue of one or more, the sum of x and y not exceeding 50; and whereinR₁ and R₂ may be the same or different, and may be selected from thegroups consisting of H--, CH₃ --, C₁ -C₁₀ straight- or branched-chainalkyl or alkenyl radicals, a phenyl group, benzyl group or a halogenatedalkyl group. Another preferred polyalkoxylated amine includes thecompound Ethomeen® EA-80 polyethoxylated ether amine, which ismanufactured by the combination of a C₈ and C₁₀ branched-chain alcoholand which is also available from Akzo Chemie America, Chicago, Ill.These preferred ether amines are selected from the group consisting of:##STR8## wherein R₇ is selected from the group of C₁ -C₂₀ alkyl groups,and R₈ is a C₂ to C₅ alkyl group; R₁ and R₂ are the same or differentand may be selected from the groups consisting of H--, CH₃ --, C₁ to C₁₀straight- or branched-chain alkyl or alkenyl radicals, a phenyl group, abenzyl group, or a halogenated alkyl group; and x and y are integerseach having a value of at least 1 and having a sum not exceeding 50.

Also required for the polyol blend are polyalkoxylated quaternaryammonium borate esters. These compounds are of the general formula:##STR9## wherein R₃ is a straight- or branched-chain alkyl or alkenylradical having from 1 to 30 carbon atoms, inclusive, or a phenyl orbenzyl radical; R₄ is H--, a C₁ to C₁₀ straight- or branched-chain alkylor alkenyl radical, a phenyl group, a benzyl group, or a halogenatedalkyl group; R₅ and R₆ are different or the same and are selected fromthe group including H--, or a C₁ to C₁₀ straight- or branched-chainalkyl or alkenyl radical, a phenyl group, or a benzyl group, and whereinm is an integer between 0 and 30, inclusive. The cationic portion of thepolyalkoxylated quaternary ammonium borate ester may also be selectedfrom the group described by the general formula: ##STR10## wherein m andR₄ are as defined hereinabove, R₉ is a C₁ -C₂₀ alkyl or alkoxy group,and R₁₀ is a C₂ to C₅ alkyl group. Preferably, R₁₀ is --C₃ H₆ -- and R₉is a combination of approximately equal amounts of C₁₂ -C₁₅ alkylgroups. In this specification, the cationic portion of thepolyalkoxylated quaternary ammonium borate esters may be selected fromeither of the above two general formulae. The weight ratio of thepolyalkoxylated amine to the polyalkoxylated quaternary ammonium borateester is between 1:0.005 and 1:12.

At least 40% by weight of the polyol blend will comprise a resin polyol,and at least 70% by weight of this resin polyol will be a combination ofpolymers and monomers having the general formula: ##STR11## wherein n isbetween 0 and 50, R₁₁ is either H-- or CH₃ --, and p and q are integerseach having a value of between 1 and 10. The "ortho-" form of thepresent combination of polymers and monomers is shown in the abovegeneral formula. It will be understood by those skilled in the art thatthe "para-" form of this combination may also be used. The monomericform of the above compounds is that form wherein n is equal to 0, andthe polymeric form of the above compounds is that form wherein n isbetween 1 and 50, inclusive. Examples of the above resin polyols includethe Terate® 200 series resin polyols for rigid and semi-rigidpolyurethane foam described in Bulletin OR-255 of Hercules, Inc.,Wilmington, Del. 19899, and the above formula (I) is believed to be anaccurate structural respresentation of about 70% of the weight of theTerate® resin polyols. The Terate® resin polyols are general purpose,moderate viscosity, aromatic polyester polyols derived from polycarbo-methoxy-substituted diphenyls, polyphenyls, and benzyl esters of thetoluate family. The Terate® polyols are dark colored, highly polarliquids that are insoluble in aliphatic hydrocarbon solvents and water.Product grades and typical properties are as follows:

                  TABLE 1                                                         ______________________________________                                                          Hy-                     dro- Acid Wa-                                Viscosity                                                                              xyl     Number as                                                                             ter, Average                                Product  at 25    Num-    Carboxylic                                                                            Per- Equivalent                             Grade    C., cps  ber     Acid    cent Weight                                 ______________________________________                                        Terate ® 202                                                                        1,900   440     4.5     0.1  127.5                                  Terate ® 203                                                                       19,000   315     5.1     0.1  178                                    Terate ® 204                                                                       13,000.sup.(a)                                                                         275     6       0.1  204                                    Terate ® 211                                                                       18,000   540     3       0.1  104                                    Terate ® 213                                                                       30,000   315     3       0.1  178                                    ______________________________________                                         .sup.(a) at 40° C.                                                

A most preferred Terate® resin polyol for use in the present inventionis Terate® 203 resin polyol.

The remainder of the polyol blend, if the total polyol blend will not belimited to the polyalkoxylated amine, polyalkoxylated quaternaryammonium borate ester, and resin polyol, will be a conventionalpolyether or polyester polyol. These polyether or polyester polyols arewell known in the art of polyurethane and polyisocyanurate foammanufacture, as for example the Voranol® polyether polyols manufacturedby the Dow Chemical Company, Midland, Mich. A most preferred polyetheror polyester polyol is Voranol® 575.

The particular polyol blend in accordance with this invention isadvantageous in that all of the components of the "B" side may beblended together with a polyol blend and the "B" side will thereafterremain a homogeneous liquid without phase separation and without theneed for agitation for at least 3 days, and may still be used tomanufacture a foam having excellent physical properties.

There are several criteria to be noted in determining whether a foam isof an acceptable quality. Of lesser importance is the tack free time,which is preferably about 60 seconds or less. Dimensional stability ismore important, and the foam should not exceed 115% of its originaldimensions after seven days. Dimensional stability is tested at twoconditions: 158° F. and 100% relative humidity; and 200° F. and ambienthumidity. Another important criterion is the percentage of closed cellsin the foam itself, with a minimum of 85% required. Finally, a percentfriability, the loss of weight of the polyisocyanurate foam due tocrumbling, is determined by the ASTM C421 test. The friability of a foamis good if under 20% and excellent if under 10%.

The following examples will demonstrate the use of the present polyolblend in the manufacture of polyisocyanurate foams using low cost resinpolyols. The first four examples pertain to the manufacture of theparticular mixture of a polyalkoxylated amine and a polyalkoxylatedquaternary ammonium borate ester. These mixtures are used in thisinvention in an amount comprising at least 5% (wt.) of the polyol blend.

EXAMPLE 1

304 grams of 1,2-propanediol (4.0 gram moles) are added to 124 grams ofboric acid (2.0 gram moles) in a one-liter, three neck flask equippedwith a heating mantle, a Dean-Stark trap, and a condenser. The mixtureis heated to 128° C. at atmospheric pressure, and retained at thattemperature and pressure for about 31/2 hours, during which time about44.5 grams of water was stripped from the mixture. A water aspirator isthen started to create a slight vacuum at the condenser, and another65.0 grams of water is stripped from the mixture during the next 53/4hours. The total water removed (109.5 grams) corresponds to thestoichiometric amount, but analysis of the borate ester adduct remainingin the flask showed that it contained 3.4% water.

40 grams (0.25 gram moles) of the borate ester formed are added to 262grams (1.0 gram mole) of Armeen® TM 97 aliphatic amine, so as to obtaina 1:0.25 ratio of amine to borate ester, and 58.1 grams of diethyleneglycol, a solvent. After heating the reaction mixture to 75° C., 121.0grams (2.75 gram moles) of ethylene oxide are added thereto over thenext 21/2 hours. Analysis of the resulting mixture showed a blendcontaining 45.4% free amine and 36.7% of a quaternary ammonium propyleneglycol borate ester having the formula: ##STR12## This formulacorresponds to Armol™ 101B-3 polyethoxylated amine/ammonium borate esterblend.

EXAMPLE 2

A 100 gallon Monel reactor was charged with 186 lbs. (0.71 lb. mole) ofArmeen® TM 97 aliphatic amine and 30.0 lbs of diethylene glycol, and themixture was heated to 65° C. Over a two hour period, 85 lbs. (0.53 lb.mole) of the bis-propylene glycol borate ester described in Example 1was pumped into the reactor, causing the temperature to rise to 80° C.After cooling to 75° C., 133 lbs. (3.02 lb. mole) of ethylene oxide wasadded over a period of two hours and 42 minutes. During this time thetotal reactor pressure was not allowed to exceed 50 psig and thetemperature was maintained at 95° C. The mixture was allowed to digestfor another 2 hours and 40 minutes, where upon analysis showed 1.317meq/g of quat and 0.307 meq/g of free amine and 0.3% H₂ O. The reactorwas purged with a stream of nitrogen at 75°-85° C. and 0 psig pressurefor 4 hours and an additional 6 hours at 100° C. Analysis showed 0.11%H₂ O. This is Armol™ 101B-1.

27.9 lbs. of the 101B-1 and 107.1 lbs. Ethomeen® T/15 were mixed in a 30gallon Pfaudler reactor at 70° C. Water was removed from the blend bysparging with a stream of nitrogen at 70° C. at 27" Hg vacuum over a51/2 hour period. Analysis after this time showed; quat 0.238 meq/g,free amines 1.779 meq/g, pH (10% in H₂ O) 10.9, H₂ O<0.1% and OH value318. This product corresponds to Armol™ 201B-125 amine/ammonium borateester blend.

EXAMPLE 3

39.0 lbs. of Armol™ 101B-1 amine/ammonium borate ester blend and 96.0lbs. of Ethomeen® T/15 ethoxylated amines was blended at 70° C. in a 30gallon Pfaudler reactor. Water was removed by sparging with a stream ofnitrogen at 70° C. 27" Hg vacuum over 5 hours. Analysis showed; quat0.331 meq/g, free amine 1.650 meq/g, pH (10% in water) 10.9, H₂ O<0.1%,OH value 332. This product corresponds to Armol™ 201B-135 amine/ammoniumborate ester blend.

Armol™ 201B-105, Armol™ 201B-145, Armol™ 201B-155 and Armol™ 201B-175amine/ammonium borate ester blend are manufactured in the mannerdescribed above using Armol™ 101B-1:Ethomeen® T/15 ratios of 10:1049,4.8:8.2, 5.9:7.1, and 9.3:5.7, respectively.

EXAMPLE 4

304 grams of 1,2-propane diol (4.0 gram moles) are added to 124 grams ofboric acid (2.0 gram moles) in a one-liter, three neck flask equippedwith a heating mantle, a Dean Stark trap, and a condenser. The mixtureis heated to 128° C. at atmospheric pressure, and retained there forabout 31/2 hours, during which time about 44.5 grams of water arestripped from the mixture. A water aspirator is then started so as tocreate a slight vacuum at the condenser, and another 65.0 grams of wateris stripped from the mixture during the next 53/4 hours. The total waterremoved of 109.5 grams corresponds to the stoichiometric amount, butanalysis of the adduct remaining in the flask showed that it contained3.4% water.

160 grams (1.0 gram mole) of this propylene glycol borate ester areadded to 262 grams (1.0 gram mole) of Armeen® TMD aliphatic amine and134 grams (1.0 gram mole) of dipropylene glycol, a solvent. The reactorin which these reactants are blended is communicative with an ethyleneoxide reservoir through a stainless steel tube. Four moles of ethyleneoxide, pressurized in its reservoir by nitrogen, are slowly added to thereactor over the next 81/2 hours, and the resulting quaternary isrepresented by the formula: ##STR13## The product formed in the aboveethoxylation comprises 48.6% of the ethoxylated quaternary ammoniumborate ester shown above and 10.3% free amine, and corresponds to Armol™101B-4 amine/quaternary ammonium borate ester.

Armol™ 101B-2 quaternary ammonium borate ester may be manufactured byadding 75 grams (0.469 gram moles) of the propylene glycol borate esterdescribed in the first paragraph of this example to 246 grams (0.939gram moles) Armeen® TM-97, and 35 grams of diethylene glycol, and thenethoxylating this blend with 144 grams (4.0 gram moles) of ethyleneoxide in the manner described in the first paragraph of this example to246 grams (0.939 gram moles) Armeen® TM-97, and 35 grams of diethyleneglycol, and then ethoxylating this blend with 144 grams (4.0 gram moles)of ethylene oxide in the manner described in the second paragraph ofthis example.

The ratios of free amine to quaternary in the presently usedamine/quaternary ammonium borate ester blend are as follows:

    ______________________________________                                        Amine/quaternary ammonium                                                                        Ratio, free amines:                                        borate ester blend quat                                                       ______________________________________                                        Armol ™                                                                    101B-1             1:4.06                                                     101B-2             1:1.51                                                     101B-3             1:0.54                                                     101B-4             1:11.6                                                     Armol ™                                                                    201B-105           1:0.005                                                    201B-125           1:0.137                                                    201B-135           1:0.234                                                    201B-145           1:0.357                                                    201B-155           1:0.490                                                    201B-175           1:0.861                                                    ______________________________________                                    

EXAMPLE 5

A urethane-modified polyisocyanurate foam was manufactured by blending170.3 grams of Mondur MR with a "B" side comprising 20 grams of Armol™201B-125, 67.5 grams Terate® 203, 12.5 grams Voranol® 575, 2.5 grams DowCorning DC-193, and 41 grams Freon® 11A. The resulting foam had a creamtime of 24 seconds, a gel time of 46 seconds, a tack free time of 69seconds, a density of 2.08 lbs. per cubic foot, a 1.21% friability,88.3% closed cells, was at 109.41% of its original dimensions afterseven days at 158° F. and 100% relative humidity, and was at 106.81% ofits original dimensions after seven days at 200° F. and the ambientrelative humidity.

EXAMPLES 6-9

Urethane-modified diisocyanurate foams were manufactured insubstantially the same manner set forth in Example 5, except thatinstead of Armol™ 201B-125, other amine/quaternary ammonium borate esterblends were used in accordance with the data in Table 2 below. Thereaction profile, densities, percent closed cells, and percentfriability are also shown in Table 2.

EXAMPLES 10-11

Urethane-modified polyisocyanurate foams were prepared by blending 20grams of a amine/ammonium borate ester blend with Terate® 203. Theparticular amine/quaternary ammonium borate ester blend used and thereaction profiles and physical properties of the foams manufactured aredisclosed in Table 3 below.

EXAMPLES 12-14

In the following examples, the "B" side, comprising the polyol blend,surfactant, a blowing agent, and a catalyst were blended and allowed tostand without agitation for seven days. At the end of the seven days,the blends were observed to determine whether they had remainedhomogeneous. Non-homogeneity, or phase separation of the "B" sides,which were stored in a sealed one-pint jar on a shelf, could be easilydetermined by viewing the blend. Upon phase separation, the "B" sidewould be seen to contain separate and distinct layers. The results arelisted in Table 4; those samples showing homogeneity are indicated bythe word "yes" in the row entitled "One Week Stability".

EXAMPLE 15

This example is substantially similar to Examples 12-14, except thathere the "B" side contain no polyester or polyether polyol and nocatalyst. Instead, the "B" side contain 20 grams of Armol™ 201B-125 and80 grams of Terate® 203 as the polyol blend, and 38.5 grams of Freon®11A. The blend remained in a stable and homogeneous form for seven dayswithout agitation.

EXAMPLES 16-17

Urethane-modified polyisocyanurate foams were manufactured insubstantially the same manner as set forth in Example 5, except thatinstead of Armol™ 201B-125, Armol™ 101B-1 and Armol™ 201B-135 were usedin accordance with the data in Table 5 below. The reaction profile,densities, percent closed cells and percent friability are also shown inTable 5. The "B" sides used in the manufacture of all of the previousfoams in Examples 5-15, pass the seven day stability test.

EXAMPLE 18

A urethane-modified polyisocyanurate foam can be manufactured insubstantially the same manner as set forth in Example 5, by substitutingArmol™ 201B-105 for Armol™ 201B-125 in the amounts in Table 6 below. Thereaction profile can be obtained as before. The "B" side blend should bestable and homogeneous for at least three days without agitation.

                                      TABLE 2                                     __________________________________________________________________________                        Example 6                                                                           Example 7                                                                           Example 8                                                                           Example 912                             __________________________________________________________________________    Armol 201B-135      17.5  --    --    --                                      Armol 201B-145      --    15    --    --                                      Armol 201B-155      --    --    15.0  --                                      Armol 201B-175      --    --    --    --                                      Terate 203          67.5  67.5  67.5  67.5                                    Voranol 575         15    17.5  17.5  17.5                                    DC-193              2.5   2.5   2.5   2.5                                     Freon 11A           42    43    43    41.5                                    Mondur MR           175.2 180.6 182.6 186.6                                   NCO/OH Ratio        2.0   2.0   2.0   2.0                                     Reaction Profile (Min:Sec)                                                    Cream Time          0:25  0:29  0:27  0:19                                    Gel Time            0:43  0:49  0:43  0:29                                    Tack Free Time      1:03  1:18  0:58  0:33                                    Density (PCF)       1.99  2.00  2.02  2.02                                    Humid Aging, 158 F/100% RH                                                                    1 day                                                                             5.73  8.25  5.66  6.30                                    % change in volume                                                                            7 days                                                                            7.06  10.05 6.70  6.71                                    Dry Aging, 200 F/ambient RH,                                                                  1 day                                                                             1.69  1.71  0.72  1.89                                    % change in volume                                                                            7 days                                                                            3.39  3.50  2.01  3.23                                    % Closed Cells      93.3  90.4  90.9  92.8                                    % Friability        0.9   1.95  0.62  0                                       __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                                            Ex-                                                                           ample 10                                                                             Example 11                                         ______________________________________                                        Armol 201B-125            20       --                                         Armol 201B-135            --       20                                         Terate 203                80       80                                         DC-193                    2.5      2.5                                        Freon 11A                 38.5     38.5                                       Mondur MR                 151.3    152.6                                      NCO/OH Ratio              2.0      2.0                                        Reaction Profile (Min:Sec)                                                    Cream Time                0:24     0:19                                       Gel Time                  0:50     0:34                                       Tack Free Time            1:23     0:53                                       Density (PCF)             2.09     2.07                                       Humid Aging, 158 F/100% RH,                                                                     1 day   16.77    6.00                                       % Change in volume                                                                              7 days  18.27    8.54                                       Dry Aging, 200 F/ambient RH,                                                                    1 day   3.84     3.44                                       % change in volume                                                                              7 days  6.72     5.73                                       % Closed Cells            92.7     92.7                                       % Friability              1.1      0.1                                        ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                   Example 12                                                                            Example 13  Example 14                                     ______________________________________                                        Armol 101B-1 10        --          --                                         Armol 101B-2 --        10          --                                         Armol 201B-125                                                                             --        --          10                                         Terate 203   45        45          45                                         Voranol 575  45        45          45                                         DC-193       2.5       2.5         2.5                                        T-45         0.5       0.5         0.5                                        Freon 11A    50.5      48          48                                         One Week Stability                                                                         YES       YES         YES                                        ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                                            Ex-                                                                           ample 16                                                                             Example 17                                         ______________________________________                                        Armol 101B-1              --       15.0                                       Armol 201B-135            10.0     --                                         Terate 203                45.0     67.5                                       Voranol 575               45.0     17.5                                       T-45                      0.5      0.5                                        DC-193                    2.5      2.5                                        Freon 11A                 57       60.0                                       Mondur MR                 275      293.6                                      NCO/OH Ratio              2.50     3.0                                        Reaction Profile (Min:Sec)                                                    Cream Time                0:36     0:17                                       Gel Time                  1:13     0:21                                       Tack Free Time            1:48     0:25                                       Density (PCF)             1.78     1.94                                       Humid Aging, 158 F/100% RH,                                                                     1 day   5.1      4.9                                        % Change in volume                                                                              7 days  4.9      5.7                                        Dry Aging, 200 F/ambient RH,                                                                    1 day   1.2      2.7                                        % change in volume                                                                              7 days  1.5      3.7                                        % Closed Cells            85.0     90.7                                       % Friability              5.2      1.7                                        ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                                      Example 18                                                      ______________________________________                                        Armol 201B-105  20.0                                                          Terate 203      67.5                                                          Voranol 575     12.5                                                          T-45            0.5                                                           DC-193          2.5                                                           Freon 11A       40.1                                                          Mondur MR       163.7                                                         NCO/OH Ratio    2.0                                                           ______________________________________                                    

What is claimed is:
 1. A method for the manufacture of urethane-modifiedpolyisocyanurate foams, comprising blending an isocyanate with a "B"side, said "B" side comprising a polyol blend, a surfactant, a blowingagent, said polyol blend comprising:(a) at least 5% (wt.) of a mixtureof a polyalkoxylated amine and a polyalkoxylated quaternary ammoniumborate ester, the weight ratio of said polyalkoxylated amine to saidpolyalkoxylated quaternary ammonium borate ester being between 1:0.005and 1:12; (b) at least 40% (wt.) of a resin polyol, said resin polyolcomprising at least 70% (wt.) of a combination of polymers and monomershaving the general formula: ##STR14## wherein n is between 0 and 50, R₁₁is either H-- or CH₃ --, and p and q are each integers between 1 and 10;and (c) the remainder of said polyol blend being a polyether orpolyester polyol.
 2. The method as set forth in claim 1, wherein saidpolyalkoxylated amine is selected from the group consisting of ##STR15##wherein R is selected from the group of alkyl radicals having between 1and 18 carbon atoms, x and y are integers each having a value of atleast one and wherein the sum of x and y does not exceed 50 and whereinR₁ and R₂ may be the same or different and may be selected from thegroups consisting of H--, CH₃ --, C₁ -C₁₀ straight- or branched-chainalkyl or alkenyl radicals, a phenyl group, a benzyl group or halogenatedalkyl group.
 3. The method as set forth in claim 2, wherein R is thetallow alkyl group, R₁ and R₂ are each H--, and wherein x plus y equal5.
 4. The method as set forth in claim 1, wherein said polyalkoxylatedquaternary ammonium borate ester is of the general formula: ##STR16##wherein R₃ is a straight- or branched-chain alkyl or alkenyl radicalhaving from 1 to 30 carbon atoms, inclusive, or a phenyl or benzylradical; R₄ is H--, a C₁ to C₁₀ straight- or branched-chain alkyl oralkenyl radical, a phenyl group, R₅ and R₆ are different or the same andare selected from the group including H--, or a C₁ to C₁₀ straight- orbranched-chain alkyl or alkenyl radical, a phenyl group, or a benzylgroup, and wherein m is an integer between 0 to 30, inclusive.
 5. Thecompound as set forth in claim 4, wherein R₃ is a straight- orbranched-chain alkyl or alkenyl radical having from 8 to 18 carbonatoms, and R₄ is H--.
 6. The compound as set forth in claim 4, whereinR₅ and R₆ are H--.
 7. The compound as set forth in claim 4, wherein R₅is H-- and R₆ is CH₃ --.
 8. The compound as set forth in claim 6,wherein m is
 0. 9. The compound as set forth in claim 7, wherein m is 0.10. The compound as set forth in claim 8, wherein R₃ is C₁₈ H₃₇ --. 11.The method as set forth in claim 1, wherein said polyalkoxylated amineis selected from the group consisting of ##STR17## wherein R₇ isselected from the group of C₁ -C₁₀ alkyl groups and R₈ is a C₂ to C₅alkyl group; R₁ and R₂ are the same or different and may be selectedfrom the groups consisting of H--, CH₃ --, C₁ to C₁₀ straight- orbranched-chain alkyl or alkenyl radicals, a phenyl group, a benzylgroup, or a halogenated alkyl group; and x and y are integers eachhaving a value of at least 1 and a sum not exceeding
 50. 12. The methodas set forth in claim 1, wherein said polyalkoxylated quaternaryammonium borate ester is of the general formula: ##STR18## wherein R₄ isH--, a C₁ to C₁₀ straight- or branched-chain alkyl or alkenyl radical, aphenyl group, a benzyl group, or a halogenated alkyl group; R₅ and R₆are different or the same and are selected from the group including H--,or a C₁ to C₁₀ straight- or branched-chain alkyl or alkenyl radical, aphenyl group, or a benzyl group, m is an integer between 0 and 30,inclusive, R₉ is a C₁ -C₂₀ alkyl group, and R₁₀ is a C₂ to C₅ alkylgroup.
 13. The method as set forth in claim 1, wherein the weight ratioof said polyalkoxylated amine to said polyalkoxylated quaternaryammonium borate ester is between 1:0.1 to 1:4.
 14. The method of claim1, wherein said "B" side further comprises a catalyst.